Footwear assembly

ABSTRACT

Footwear assemblies are provided in which components comprise certain block copolymers of conjugated dienes with monovinyl arenes or their hydrogenated derivatives.

United States Patent I 72] Inventors Willis R. Hendricks [5 i] Int. ClA43b 13/06 Palos Verdes Peninsula; [50] Field of Search". Richard L.Dantorth, Harbor City, both of, Calif. 2 L 3 0.257 [56] References Cited[22] Filed Jan. 16, 1970 UNITED STATES PATENTS [45] Patented June 29,1971 2,995,839 8/1961 Cronin 36/9 [731 Asslgn" CM'PW 3,352,032 11/1967Yamaguchi 36/9 New Ymlh 3,484,959 12/1969 Torgerson 36/9Continuation-impart of application Ser. No. 698,990, Jan. 12, 1968, nowabandoned Continuation-impart of application Ser. No. 423,724, Jan. 6,1965, now abandoned.

[52] U.S.Cl

Primary ExaminerPatrick D. Lawson Anomeys-William H. Myers and Joseph W.Brown ABSTRACT: Footwear assemblies are provided in which componentscomprise certain block copoiymers of conjugated dienes with monovinylarenes or their hydrogenated derivatives.

PATENTEU JUN 2 819?:

INVENTORS'.

WILLlS R. HENDRICKS RICHARD L. DANFORTH THEIR AGENT FOOTWEAR ASSEMBLYThis application is a continuation-impart of our copending application,Ser. No. 698,990, filed Jan. 12, 1968 now abandoned, which is acontinuation-in-part of application, Ser. No. 423,724, filed Jan. 6,1965 now abandoned.

This invention relates to improvements in footwear. More particularly itrelates to the construction and assembly of shoes, boots, slippers, andthe like.

In the manufacture of footwear of various types including canvas-topshoes, leather-top shoes, rubbers, boots, and the like, it is often aproblem to develop a product having all the physical properties whichare desired. A leather sole thick enough to protect the foot isexpensive and often is too heavy for wearing comfort. A rubber sole shoemade of the ordinary rubbers requires vulcanization and has a number ofproperties which are found to be disadvantageous in footwear. Forexample, when certain vulcanized rubbers are utilized as sole componentson shoes, the sole exhibits the same flexural properties in alldirections. This results in a certain amount of curling of the edges ofthe sole along the sides thereof. On the other hand, if vulcanizedrubber solings are compounded to avoid this undesirable curling featurethen the flex of the sole is substantially reduced and the shoe isthereby too stiff for comfortable wear.

One of the major items of cost in the preparation of footwear containingthe previous utilized types of rubber com ponents is that involved inthe vulcanization of the components either before or after assembly ofthe various shoe components into a shoe shape. Not only is the cost ofthe vulcanization step per se objectionable, but, as is well known, thestamping out of shoe sole slab stock after vulcanization results in alarge amount of scrap (about 25 percent by volume) which cannot bereworked and simply must be discarded or ground for use as filler.

At the present time, the low-cost shoe market is largely restricted toplastic materials such as polyvinyl chloride shoe components which donot require vulcanization but inherently possess undesirable properties.These include a lack ofskid resistance when wet, stiffening at lowtemperatures, a lack of proper resilience, and other physical propertieswhich it would be desirable to improve.

lt is an object of the present invention to improve the construction ofshoes. It is a particular object of the invention to provide shoes andshoe components which do not require vulcanization. It is a specialobject of the invention to provide shoes having various types of solesof a particular kind of rubber as defined hereinafter which does notrequire vulcanization and which has a greater degree of flex along oneaxis than it has along an axis at right angles thereto. It is a specialobject to provide materials suitable for extrusion of shoe componentstocks which do not decompose in the extruder, lt is a special object toprovide materials for shoe component stocks which can be recycledthrough extruders and injection molding machines without deleteriouseffect on the durability of the resultant shoe component. Another objectis to provide shoe soles having high skid resistance and goodflexibility at low temperatures. An important economic objective isachieved in substantially reducing the shoe fabrication time.

Other objects will become apparent during the following detaileddescription of the invention.

FIG. 1 represents a sketch in perspective ofa typical sample of thepresent invention which in this case is embodied in a lightweightcanvas-top shoe.

FIG. 2 is a longitudinal section through the shoe to show constructionof several parts and to show in detail an optional fabrication of thesole and its relationship to the upper.

Now in accordance with the present invention, footwear and the like isprovided wherein a component thereof comprises a block copolymer of amonovinyl arene and a conjugated diene, or hydrogenated derivativesthereof.

Where, in the specification and claims reference is made to molecularweights, it will be understood that reference is made to viscosityaverage molecular weights determined by a relationship between theintrinsic viscosity of the block copolymer and osmotic molecular weight.The molecular weights so determined agree closely with molecular weightsobtained from scintillation counting of samples of the block copolymer.

While the present invention is especially directed to shoes and shoesoles as the component comprising the subject block copolymers, thelatter may be employed at any point in the shoe construction as in shoeuppers, show soles, foxing, cements, fillers, counters, laminatedcomponents, heels, inner soles, liners, and the like. The blockcopolymers may be compounded as described more fully hereinafter to suiteach of these particular utilities with advantages both in processingand in physical properties being gained.

The block copolymers to be utilized in the formation of shoes and shoecomponents may either be nonhydrogenated block copolymers or those whichhave been subjected to hydrogenation, preferably so that at least about50 percent of the original double bonds in the block copolymer arereduced thereby. Hydrogenation may be complete, random, or selective.Preferably, the diene polymer blocks are hydrogenated to eliminate atleast about percent of the aliphatic unsaturation.

The formation of the block copolymers, while not forming an essentialaspect of this invention may be briefly described for a fullerunderstanding thereof. The vinyl arenes which may be employed for thepreparation of the lblock copolymers include especially styrene,alpha-methyl styrene, vinyl toluene as well as their homologs andanalogs and mixtures thereof. The conjugated dienes useful for thepresent purpose are those preferably containing from 4 to 8 carbon atomsper molecule and preferably from 4 to 6 carbon atoms per molecule,especially butadiene and isoprene and mixtures thereof. The blockcopolymers may be formed by a number of different types of processessuch as the following:

A vinyl arene such as styrene may be polymerized in substantially inerthydrocarbon medium in the presence of a monofunctional alkali metalalkyl compound such as lithium alkyl to form an initial polymer blockcarbanion A terminated with a lithium ion. Without further treatment, aconjugated diene such as butadiene or isoprene is introduced and blockcopolymerization effected to produce the intermediate block copolymercarbanion A-B, associated with the alkali metal ion such as lithium.Finally, a vinyl arene such as styrene is introduced and polymerizationcontinued to form the desired polymer A-B-A.

A second process may be referred to as a coupling process wherein thefirst stage is as described above to form the initial polymer block Aterminated with lithium, followed by introduction of the conjugateddiene to form a polymer block thereof having a molecular weight onlyhalf of that desired in the final product. At this stage a couplingagent is then added to form the desired three-block polymer A-B-A, inthis case containing an insignificant coupling link in the center blockB. This coupling link is ignored in the generic description of the blockpolymers in this specification.

Multifunctional coupling agents may be used to form nonlinear molecules.Thus, the invention contemplates the use of linear configurations, e.g.,A(BA),,and nonlinear configurations, e.g., A-B(B-A),,wherein each A is amonovinyl arene polymer block and each B is a conjugated diene polymerblock. Any adjacent substantially identical blocks are considered as asingle block in the following discussion of molecular weights.

An optional process for the preparation of the subject block copolymerscomprises the initial formation of the center block of conjugated dieneby the use of difunctional catalyst such as dilithium naphthalene andthe like, to form the center polymer block terminated at both ends witha metallic radical such as lithium. Thereafter, the vinyl arene monomermay be injected into the system and both of the terminal blocks formedsimultaneously.

One of the essential aspects of the present invention comprises thediscovery that only a very restricted class of the subject blockcopolymers (including their hydrogenated counterparts) may be readilyemployed for the formation of shoes and their components. Therestriction is due primarily to performance and processingconsiderations since if polymers having average molecular weights lowerthan those specified hereinafter are employed the physical properties ofthe resulting block copolymers are relatively poor and lacking intensile strength. On the other hand, if the polymer blocks havemolecular weights greater than those specified hereinafter,processability of the resulting block copolymers rapidly becomesdifficult or even impossible without excessive modification withextender oils and the like which, in turn, tends to degrade the physicalproperties desired in end products.

Therefore in accordance with an essential aspect of the invention, thevinyl arene polymer blocks should have average molecular weights betweenabout 9,000 and about 30,000 and preferably between about 14,000 andabout 25,000 at the same time, the conjugated diene polymer blocksshould have average molecular weights between about 35,000 and about130,000, and preferably between about 40,000 and about 80,000, theweight ratio of vinyl arene polymer blocks to conjugated diene polymerblocks being between about 25:75 and about 60:40, usually between about30:70 and 40:60.

The ranges of molecular weights depend, within these limits, upon thetype of compositions. Thus, unfilled stocks desirably comprise polyvinylarene blocks of 9,000-15,000 molecular weight and polydiene blocks of40,000-50,000 molecular weight. Filled stocks, on the other hand, havepolyvinyl arene blocks of 12,00030,000 molecular weight and diene blocksof 50,000-80,000 molecular weight.

Another essential reason for limiting the class of block eopolymers tothose having the components and molecular weights described above, liesin the ability of the defined class to form a rubber having thestress-strain properties of a vulcanized rubber without the necessityfor going through the vulcanization step normally employed with othertypes of rubbers.

While the generic concept of the present invention comprises theutilization of the highly restricted class of block copolymers definedabove in the formation of shoes and shoe components, in many cases theblock copolymers will be modified with compounding ingredients to impartcertain physical properties desired in the finished product. This willdepend not only upon the footwear article per se but upon the method ofmanufacture. The following discussion, while restricted to thealternatives involved in various kinds of shoe soling and theirmanufacture, applies with modifications apparent to those skilled in theart of shoe manufacture to the preparation of other shoe components.Three principal types of shoe soling are particularly contemplated: Slabstock is prepared by a milling or extrusion process to form a sheet ofthe desired sole thickness. The sole shapes are then stamped out of thesheet and thereafter attached to the shoe upper. The use of the blockcopolymers of the present invention offers the advantages of easierprocessing, better ,wear, elimination of the vulcanization step,capability of recycling scrap without harming resultant shoe quality,and a peculiarity inherent in the particular block copolymers relativeto flexibility in a desired direction combined with stiffness in theperpendicular direction' More especially, the soling slab has been foundto have a greater flexibility perpendicular to (or normal to) thedirection of extrusion than it has in the direction of extrusion. Thisuseful aspect may be capitalized upon by cutting the sole shapes fromthe slab perpendicular to (or normal to) the direction of extrusion soas to obtain a sole having greater flexibility around the short axis ofthe sole combined with stiffness around the long axis of the sole, thuspreventing the undesirable curling up around the edges experienced withother types of rubber soles.

For this type of shoe soling, it is preferred to employ 100 parts byweight of the subject block copolymer, 25-125 (preferably 35-125) phr.(parts per 100 of rubber) of a polystrene; 5-90 (preferably 5-60 phr. ofa rubber extcnd- TABLE I Slab soling stocks Compound A B C Blockcopolymer 100 100 Polystyrene (crystal grade) 70 55-70 60 Soft clay(filler) 30 100 250 Low molecular weight polyalphamethyl styrene 30 50 Naphthenic oil 20 30 40 it will be noted in the above formulations thattwo types of polystyrenes are employed. The crystal grade polystyrene isutilized for its function as a reinforcing agent which is highlycompatible with the block copolymer. On the other hand, the lowmolecular weight polyalpha-methyl styrene is employed as a processingaid during the processing of the shoe sole into its slab form. 7

Other large classes of footwear are referred to as injection moldedfootwear and hand built footwear. These classes inelude not onlyfootwear such as boots and the like comprising molded articles entirelymade of a single material, but also shoe components which are moldedeither directly onto other shoe components or formed for laterattachment to the rest of the shoe. The class is especially consideredwith the preparation of boots and with canvas top shoes wherein thecanvas top is directly attached by the molding process to the blockcopolymer sole. It will be recognized by those familiar with the shoemaking art that a somewhat different type of compound is employed forthis purpose to permit ready moldability thereof at temperatures whichwill effect a strong attachment between the molded part of the shoe andany nonrubber components such as a canvas upper. Consequently, thecompositions for injection molded stock include those comprising 100parts by weight of the block copolymer, 25-1 10 (preferably 50-85) phr.of a polystyrene, 60-150 (preferably 60-150) phr. of a rubber extendingoil, and 0-150 phr. of a finely divided filler. The most effective blockpolymers for injection molded footwear have end blocks A with molecularweights of 10,000-25,000 and center blocks B with molecular weights of45,00090,000 (preferably 45,000-65,000).

Due to the method by which shoe components are formed, e.g., by moldingin this type of application, a somewhat different formulation isrequired both in the block eopolyrrter and in the component modifyingthe same. For instance, a relatively higher portion of a rubber extenderoil is employed but at the same time a block copolymer having a higherratio of the vinyl arene polymer block is utilized. The followinmulation is typical of those which may be employed for i: tion moldingpurposes.

The block copolymer employed in the above formulation waspolystyrene-polybutadiene polystyrene having block molecular weights of14,000-53,00014,000. When the block polymer had block molecular weightsof 22,000-50,000-

22,000, the oil was increased to 100 phr.

The subject block copolymer slab stock and injection molded soling havethe advantages of being capable of compounding for easily processablestocks which do not require vulcanization. Thus, it is possible to reusescrap, eliminate the scorch problems associated with vulcanization, andsimplify processing. Compared with polyvinylchloride injection moldedformulations, the formulation given above has the substantial advantagesof flexibility at low temperatures, high coefficient of friction, truerubberlike elasticity and feel, and greater stiffness for a givenhardness. The latter feature pro vides greater resistance tostone-bruising" during wear.

In addition to the above general types of soling compositions, anotherclass contemplated is that of calendered soling wherein the blockcopolymer compounds are sheeted through embossing calenders and thesoles are then cut out from the unvulcanized sheet. The sole is cementedto the upper, a binding (foxing) strip is applied and the assembled shoeis finished without the necessity for vulcanization normally required.The advantages gained are in general those described for slab stock andparticularly for injection molded soling.

While the compositions especially contemplated are those describedabove, it is also contemplated to form foam rubber shoe components suchas inner soles, laminates for outer soles, laminates to be combined withother shoe materials such as leather, polyvinylchloride and the like.The compositions may be varied with respect to the ratio ofthermoplastic (polyvinyl arene) blocks so as to provide a controlleddegree of flexibility in the end product.

The supplementary components contained in the several compounds referredto hereinabove comprise particularly polystyrenes of two general types.Those of high molecular weight, e.g., over 75,000 molecular weight arecontemplated for use as reinforcing agents while the relatively lowmolecular weight polystyrenes are useful not only in imparting stiffnessbut also as processing aids without sacrificing tensile. They may beused in conjunction with extending oils and resinlike extendersincluding coumarone-indene resins, petroleum hydrocarbon resins, rosin,phenol-formaldehyde, and glycerol esters. Processing oils include notonly esters such as dioctyl phthalate and the like but especially thehydrocarbon oils having not more than about 30 percent aromatichydrocarbon content referred to either as naphthenic or aliphatichydrocarbon oils. However, for black stocks the aromatic residual oilsmay be employed.

Summarizing the above, shoe sole compositions especially contemplatedhave the general formulation as follows:

Block copolymer as defined above 100 parts by weight, polystyrene 25-125 (preferably 35-125 phr., extending oil 5l50 (preferably 5-90 )phr.,and filler 0350 (preferably 0-300 )phr.

The fillers utilized in the compositions especially contemplated arewell known in the art and include clay, titanium dioxide, carbon blacks,whiting (calcium carbonate), and other pigments as well as fibrousfillers such as cellulosic fibers, sawdust, ground cork, etc.

in FIGS. l and 2, represents the shoe having a top formed from a forwardtoe and vamp piece 11, a body piece or instep portion 12, and the heelsection or quarter 13. This much is conventional and the parts form theuppers. The optional trim or binding 17 (foxing) gives the edges afinish; grommets finish eyelets for lacing 16. The individual parts varyas the styling is varied. The assembly of uppers is bound to the sole inthis type of shoe by and under a rubber binding called foxing whichpasses entirely around the shoe at the level of the sole, extending ashort distance onto the uppers. It is firmly adhered both to the uppersand to the sole and may comprise a plastic binding or more preferably ablock copolymer strip comprising a copolymer compound of the presentinvention.

In one type of light-shoe sole 1: ;scmbly such as illustrated in FIG. 2,the sole consists of an inner fabric or block copolymer lining 20,somewhat exaggerated in the drawing, under which is a thin layer ofsponge block copolymer rubber composition 21, which is followed by athin layer of block copolymer sheet ing 22 and 23, which is formed toprovide a somewhat thickened section at theheel 24. The outer sole 25 isa block copolymer composition of the present invention to provide awearing surface which may be flat, corrugated, or patterned in anydesired manner.

One of the items of cost in shoe manufacture relates to rate at which agiven shoe component can be formed. For example, it has been found thatslab soling stock comprising the subject block copolymers can beextruded at a rate of about 5 percent faster than a comparablepolyvinylchloride slab soling stock. In comparative tests involvinginjection molding ofa sole onto a basketball shoe upper, a polyvinylsole required total index time of 19 seconds, while a block copolymersole required 18 seconds.

We claim as my invention:

l. A footwear construction including an upper component and a solecomponent wherein at least one of said components comprises anunvulcanizedblock copolymer of the group consisting of polymers of amonovinyl arene and of a conjugated diene, and hydrogenated derivativesof said polymers wherein the original unsaturation has been reduced atleast 50 percent by hydrogenation, the monovinyl arene blocks having anaverage molecular weight between about 9,000 and about 30,000 and theconjugated diene blocks having an average molecular weight between about35,000 and about 130,000 the weight ratio of monovinyl arene polymerblocks to conjugated diene polymer blocks being between about 25:75 andabout 60:40.

2. Shoe sole comprising:

i. l00 parts by weight of an unvulcanized block copolymer having thegeneral configuration polystyrene-polybutadiene polystyrene wherein eachpolystyrene block has an average molecular weight between about 9,000and 30,000, and the polybutadiene block has an average molecular weightbetween about 35,000 and about 130,000 the weight ratio of monovinylarene polymer blocks to conjugated diene polymer blocks being betweenabout 25:75 and about 60:40;

2. 25 I25 phr. of a polystyrene having a molecular weight of at least75,000;

3. 5-90 phr. ofa rubber extending oil; and

4. 0350 phr. ofa finely divided filler.

3. An injection molded footwear comprising:

l. l00 parts by weight of an unvulcanized block copolymer having thegeneral configuration polystyrene-polybutadiene polystyrene wherein eachpolystyrene block has an average molecular weight between about 10,000and 25,000 and the polybutadiene block has an average molecular weightbetween about 40,000 and about 90,000 the weight ratio of monovinylarene polymer blocks to conjugated diene polymer blocks being betweenabout 25:75 and about 60:40;

2. 25-l l0 phr. of a polystyrene having a molecular weight of at least75,000;

3. 60 phr:ofa rubber extending oil; and

4. 0 l 50 phr. of a finely divided filler.

4. A slab shoe soling comprising:

1. I00 parts by weight of an unvulcanized block copolymer having thegeneral configuration polystyrene-polybutadiene polystyrene wherein eachpolystyrene block has an average molecular weight between about 14,000and about 25,000 and the polybutadiene block has an average molecularweight between about 85,000 and 125,000, the weight ratio of monovinylarene polymer blocks to conjugated diene polymer blocks being betweenabout 25:75 and about 40:60; 2. 25 l 25 phr. of a polystyrene having amolecular weight of at least 75,000; 3. 5-9 0 phr. ofa rubber extendingoil; and 4. 0-350 phr. ofa finely divided filler.

5. A footwear construction according to claim 1 wherein the blockcopolymer has the general configuration wherein each A is a monovinylarene polymer block and B is a conjugated diene polymer block.

6. A footwear construction according to claim 1 wherein the solecomprises an extruded block copolymer composition, the length of thesole being perpendicular to the direction of extrusion.

7. A footwear construction according to claim 1 including an uppercomponent and a sole component wherein at least one of said componentscomprises an unvulcanized block copolymer of the group consisting ofpolymers having a general configuration wherein each A is a polymerblock ofa monovinyl arene and B is a polymer block of a conjugateddiene, and hydrogenated derivatives of said polymers wherein theoriginal unsaturation has been reduced at least 50 percent byhydrogention, the monovinyl arene blocks A having an average molecularweight between about 9,000 and about 30,000 and block B having anaverage molecular weight between about 40,000 and about 80,000 theweight ratio of monovinyl arene polymer blocks to conjugated dienepolymer blocks being between about 25:75 and about 40:60.

8. Shoe sole composition comprising l. 100 parts by weight of anunvulcanized block copolymer having the general configurationpolystyrene-polybutadiene polystyrene wherein each polystyrene block hasan average molecular weight between about 9,000 and about 30,000 and thepolybutadiene block has an average molecular weight between about 40,000and about 80,000 the weight ratio of monovinyl arene polymer blocks toconjugated diene polymer blocks being between about 25:75 and about40:60;

2. 35-125 phr. of a polystyrene having a molecular weight of at least75,000;

3. 5-90 phr. of a rubber extending oil', and

4. 0-300 phr. ofa finely divided tiller.

9. An injection molded footwear composition comprising:

l. 100 parts by weight of an unvulcanized block copolymer having thegeneral configuration polystyrene-polybutadiene polystyrene wherein eachpolystyrene block has an average molecular weight between about 10,000and 20,000 and the polybutadiene block has an average molecular weightbetween about 45,000 and about 65,000 the weight ratio of monovinylarene polymer blocks to conjugated diene polymer blocks being betweenabout 25:75 and about 40:60;

2. 50-85 phr. of a polystyrene having a molecular weight of at least75,000

3. 60-90 phr. ofa rubber extending oil; and

4. 0- l 50 phr. ofa finely divided filler.

10. A slab shoe soling composition comprising:

i. 100 parts by weight of an unvulcanized block copolymer having thegeneral configuration polystyrene-polybutadiene polystyrene wherein eachpolystyrene block has an average molecular weight between about 14,000and about 25,000 and the polybutadiene block has an average molecularweight between about 65,000 and 75,000 the weight ratio of monovinylarene polymer blocks to conjugated diene polymer blocks being betweenabout 25:75 and about 40:60

2. 35-l25 phr. of a polystyrene having a molecular weight of at least75,000;

3. 5-60 phr. of a rubber extending oil; and

4. 0-300 phr. ofa finely divided filler.

11. A shoe comprising an upper component and a sole component whereinthe sole is a composition according to claim 8.

12. A composition comprising:

1. parts per weight of an unvulcanized block copolymer having thegeneral configuration wherein polystyrene wherein each polystyrene blockhas an average molecular weight between about 9,000 and about 30,000,and the polybutadierle block has an average molecular weight betweenabout 35,000 and about l30,000 the weight ratio of monovinyl arenepolymer blocks to conjugated diene polymer blocks being between about25:75 and about 60:40;

2. 25- l 25 phr. of a polystyrene having a molecular weight of at least75,000;

3. 5-90 phr. of a rubber extending oil; and

4. 0-350 phr. ofa finely divided filler.

13. A composition comprising:

1. 100 parts by weight of an unvulcanized block copolymer having thegeneral configuration polystyrene-polybutadiene polystyrene wherein eachpolystyrene block has an average molecular weight between about 10,000and 25,000 and the polybutadiene block has an average molecular weightbetween about 40,000 and about 90,000 the weight ratio of monovinylarene polymer blocks to conjugated diene polymer blocks being betweenabout 25:75 and about 60:40;

2. 25-l 10 phr. of a polystyrene having a molecular weight of at least75,000;

3. 60- l 50 phr. of a rubber extending oil; and

4. 0- l 50 phr. ofa finely divided filler.

14. A composition comprising:

1. 100 parts by weight of an unvulcanized block copolymer having thegeneral configuration polystyrcne-polybutadiene polystyrene wherein eachpolystyrene block has an average molecular weight between about 14,000and about 25,000 and the polybutadicne block has an average molecularweight between 85,000 and 125,000, the weight ratio otmonovinyl arenepolymer blocks to conjugated diene polymer blocks being between about25:75 and about 40:60;

2. 25- l 25 phr. of a polystyrene having a molecular weight of at least75,000;

3. 5-90 phr. ofa rubber extending oil; and

3. 0-350 phr. of a finely divided filler.

1. A footwear construction including an upper component and a solecomponent wherein at least one of said components comprises anunvulcanized-block copolymer of the group consisting of polymers of amonovinyl arene and of a conjugated diene, and hydrogenated derivativesof said polymers wherein the original unsaturation has been reduced atleast 50 percent by hydrogenation, the monovinyl arene blocks having anaverage molecular weight between about 9,000 and about 30,000 and theconjugated diene blocks having an average molecular weight between about35,000 and about 130,000 the weight ratio of monovinyl arene polymerblocks to conjugated diene polymer blocks being between about 25:75 andabout 60:40.
 2. Shoe sole comprising:
 2. 25-125 phr. of a polystyrenehaving a molecular weight of at least 75,000;
 2. 35-125 phr. of apolystyrene having a molecular weight of at least 75,000;
 2. 25-110 phr.of a polystyrene having a molecular weight of at least 75,000;
 2. 50-85phr. of a polystyrene having a molecular weight of at least 75,000 2.35-125 phr. of a polystyrene having a molecular weight of at least75,000;
 2. 25-125 phr. of a polystyrene having a molecular weight of atleast 75,000;
 2. 25-110 phr. of a polystyrene having a molecular weightof at least 75,000;
 2. 25-125 phr. of a polystyrene having a molecularweight of at least 75,000;
 3. 5-90 phr. of a rubber extending oil; and3. 0-350 phr. of a finely divided filler.
 3. An injection moldedfootwear comprising:
 3. 60-150 phr. of a rubber extending oil; and 3.5-90 phr. of a rubber extending oil; and
 3. 5-60 phr. of a rubberextending oil; and
 3. 60-90 phr. of a rubber extending oil; and 3.60-150 phr. of a rubber extending oil; and
 3. 5-90 phr. of a rubberextending oil; and
 3. 5-90 phr. of a rubber extending oil; and
 4. 0-350phr. of a finely divided filler.
 4. 0-300 phr. of a finely dividedfiller.
 4. 0-150 phr. of a finely divided filler.
 4. A slab shoe solingcomprising:
 4. 0-150 phr. of a finely divided filler.
 4. 0-300 phr. of afinely divided filler.
 4. 0-350 phr. of a finely divided filler. 4.0-150 phr. of a finely divided filler.
 5. A footwear constructionaccording to claim 1 wherein the block copolymer has the generalconfiguration A-B-A wherein each A is a monovinyl arene polymer blockand B is a conjugated diene polymer block.
 6. A footwear constructionaccording to claim 1 wherein the sole comprises an extruded blockcopolymer composition, the length of the sole being perpendicular to thedirection of extrusion.
 7. A footwear construction according to claim 1including an upper component and a sole component wherein at least oneof said components comprises an unvulcanized block copolymer of thegroup consisting of polymers having a general configuration A-B-Awherein each A is a polymer block of a monovinyl arene and B is apolymer block of a conjugated diene, and hydrogenated derivatives ofsaid polymers wherein the original unsaturation has been reduced atleast 50 percent by hydrogention, the monovinyl arene blocks A having anaverage molecular weight between about 9,000 and about 30,000 and blockB having an average molecular weight between about 40,000 and about80,000 the weight ratio of monovinyl arene polymer blocks to conjugateddiene polymer blocks being between about 25:75 and about 40:60.
 8. Shoesole composition comprising
 9. An injection molded footwear compositioncomprising:
 10. A Slab shoe soling composition comprising:
 11. A shoecomprising an upper component and a sole component wherein the sole is acomposition according to claim
 8. 12. A composition comprising:
 13. Acomposition comprising:
 14. A composition comprising: